TWI601249B - Cooling structure - Google Patents
Cooling structure Download PDFInfo
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- TWI601249B TWI601249B TW102145992A TW102145992A TWI601249B TW I601249 B TWI601249 B TW I601249B TW 102145992 A TW102145992 A TW 102145992A TW 102145992 A TW102145992 A TW 102145992A TW I601249 B TWI601249 B TW I601249B
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- resin composition
- heating element
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0203—Cooling of mounted components
- H05K1/0209—External configuration of printed circuit board adapted for heat dissipation, e.g. lay-out of conductors, coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/284—Applying non-metallic protective coatings for encapsulating mounted components
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
- H01L23/3121—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/06—Thermal details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10227—Other objects, e.g. metallic pieces
- H05K2201/10371—Shields or metal cases
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10431—Details of mounted components
- H05K2201/10507—Involving several components
- H05K2201/10545—Related components mounted on both sides of the PCB
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
- H05K2203/1305—Moulding and encapsulation
- H05K2203/1327—Moulding over PCB locally or completely
Description
本發明係關於一種用於電子設備、精密設備等的散熱結構體。 The present invention relates to a heat dissipation structure for an electronic device, a precision device, or the like.
近年來，個人電腦、行動電話、PDA(Personal Digital Assistant，個人數位助理)等電子設備或LED(Light-Emitting Diode，發光二極體)、EL(Electroluminescence，電致發光)等照明及顯示設備等之性能之提高較為顯著，其原因在於運算元件或發光元件之性能之提高較為顯著。如此隨著運算元件或發光元件之性能提高，發熱量亦顯著增加，成為電子設備、照明、顯示設備之誤動作或電子零件之損傷的一個原因，其散熱對策成為較大之問題。同時個人電腦、行動電話等電子設備就防止使用時之燒傷之觀點而言，重要為使熱向不與人體接觸之部位傳導，而關於與人體接觸之部位則不使熱向外傳導。 In recent years, electronic devices such as personal computers, mobile phones, PDAs (Personal Digital Assistants), LEDs (Light-Emitting Diodes), EL (Electroluminescence), and other lighting and display devices. The improvement in performance is remarkable because the performance of the arithmetic element or the light-emitting element is significantly improved. As the performance of the arithmetic element or the light-emitting element is increased, the amount of heat generation is remarkably increased, which is a cause of malfunction of the electronic device, the illumination, the display device, or damage of the electronic component, and the heat dissipation countermeasure becomes a big problem. At the same time, in view of the prevention of burns in the use of electronic devices such as personal computers and mobile phones, it is important that heat is transmitted to a portion that is not in contact with the human body, and that the portion that is in contact with the human body does not conduct heat outward.
作為此種電子零件之散熱對策，已知有如專利文獻1所示之使用導熱性樹脂成形體者、如專利文獻2~4所示之使用散熱片材之技術。若使用成形體，則存在會產生重新對每個構件改做模具等之勞力時間的問題。又，不僅限於電性‧電子零件，許多發熱體或散熱體之表面不平滑，故若使用散熱片材則散熱用構件無法與發熱體及散熱體密接，從而與發熱體或散熱體之間的接觸面積會減少。於此種印刷基板上使用大大小小各種尺寸之電子零件，若使用散熱片材等散熱構件則無法追隨微細之凹凸。因此存在由於接觸面積之減少，自發熱體向散熱體之熱傳導效率會下降，從而散熱用構件所具有之散熱性能無法充 分地發揮之問題。 As a countermeasure against heat dissipation of such an electronic component, a technique using a heat-conductive resin molded body as disclosed in Patent Document 1 and a heat-dissipating sheet as disclosed in Patent Documents 2 to 4 are known. When a molded body is used, there is a problem that labor time for reworking a mold or the like for each member is generated. Moreover, it is not limited to electrical and electronic components, and the surface of many heat generating bodies or heat radiating bodies is not smooth. Therefore, if a heat radiating sheet is used, the heat radiating member cannot be in close contact with the heat generating body and the heat radiating body, and thus is connected to the heat generating body or the heat radiating body. The contact area will decrease. When electronic components of various sizes and sizes are used on such a printed circuit board, if a heat dissipating member such as a heat radiating sheet is used, fine irregularities cannot be followed. Therefore, due to the decrease in the contact area, the heat transfer efficiency of the self-heating body to the heat sink is lowered, and the heat dissipation performance of the heat radiating member cannot be charged. The problem of playing the land.
又，於專利文獻5中揭示有為了減小散熱性之不均、高效率地散熱而將印刷基板正面及背面之電子零件埋入至散熱性樹脂中之技術。然而所揭示之樹脂為導電性橡膠，故額外需要於塗佈散熱樹脂後進而於印刷基板之正面及背面進而設置絕緣層之步驟。進而藉由於印刷基板之正面及背面塗佈樹脂，熱會向所有方向傳導，從而無法規定散熱之方向，故於電子設備使用時會傳熱至與人體接觸之部位，從而存在使用時之燒傷之危險性。 Further, Patent Document 5 discloses a technique of embedding electronic components on the front and back sides of a printed circuit board into a heat-dissipating resin in order to reduce uneven heat dissipation and efficiently dissipate heat. However, since the disclosed resin is a conductive rubber, it is necessary to further provide a step of further providing an insulating layer on the front and back surfaces of the printed substrate after applying the heat-dissipating resin. Furthermore, since the resin is applied to the front and back surfaces of the printed substrate, heat is transmitted in all directions, and the direction of heat dissipation cannot be specified. Therefore, when the electronic device is used, heat is transferred to a portion in contact with the human body, and there is a burn at the time of use. Dangerous.
進而，作為以使熱於內部之固定之位置散掉，而不向外部傳熱為目的之散熱對策，於專利文獻6中記載有連接配置有電子零件之發熱基板與基底基板，使電子零件之發熱向基底基板傳導之技術。然而，由於需要複數塊基板，對於期望小型化‧薄型化之電子設備則難以確保空間，同時需要大幅度地進行設計變更。 Further, as a heat-dissipating measure for the purpose of dissipating the heat to the inside, and not transferring the heat to the outside, Patent Document 6 describes a heat-generating substrate and a base substrate on which electronic components are connected, and the electronic components are used. The technique of heat conduction to the base substrate. However, since a plurality of substrates are required, it is difficult to secure a space for an electronic device that is desired to be miniaturized and thinned, and it is necessary to make a large design change.
專利文獻1：日本專利特開2011-126262號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2011-126262
專利文獻2：日本專利特開2002-305271號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-305271
專利文獻3：日本專利特開2011-165699號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2011-165699
專利文獻4：日本專利特開2008-153704號公報 Patent Document 4: Japanese Patent Laid-Open Publication No. 2008-153704
專利文獻5：日本專利特開2009-016605號公報 Patent Document 5: Japanese Patent Laid-Open Publication No. 2009-016605
專利文獻6：日本專利特開2009-059760號公報 Patent Document 6: Japanese Patent Laid-Open Publication No. 2009-059760
本發明之目的在於提供一種散熱結構體，其對於要求小型化‧薄型化之電子設備，可於不變更積體電路或其周邊部位之設計之情況下有效地使發熱體(電子零件)之熱散掉，且防止電子設備表面局部地 成為高溫。 An object of the present invention is to provide a heat dissipating structure which can effectively heat a heating element (electronic part) without changing the design of the integrated circuit or its peripheral portion in an electronic device which is required to be miniaturized and thinned. Dissipate and prevent the surface of the electronic device from being partially Become high temperature.
本發明為了解決上述課題而採用以下方法。 In order to solve the above problems, the present invention adopts the following method.
1)本發明係一種散熱結構體，其特徵在於：其係具有(A)印刷基板、(B)第1發熱體、(C)第2發熱體以及(D)導熱性硬化性液狀樹脂組合物之硬化物者，印刷基板(A)具有第1面及位於第1面之相反側之第2面，第1發熱體(B)配置於第1面上，第2發熱體(C)配置於第2面上，第1發熱體(B)之發熱量為第2發熱體(C)之發熱量以上，於第2發熱體(C)之周圍配置導熱性硬化性液狀樹脂組合物之硬化物(D)，於第1發熱體(B)之周圍配置導熱率低於導熱性硬化性液狀樹脂組合物之硬化物(D)的層。 1) The present invention relates to a heat dissipating structure comprising (A) a printed substrate, (B) a first heating element, (C) a second heating element, and (D) a thermally conductive curable liquid resin combination In the cured material, the printed circuit board (A) has a first surface and a second surface on the opposite side of the first surface, and the first heating element (B) is disposed on the first surface, and the second heating element (C) is disposed. In the second surface, the heat generation amount of the first heat generating element (B) is equal to or higher than the heat generation amount of the second heat generating element (C), and the heat conductive curable liquid resin composition is disposed around the second heat generating body (C). In the cured product (D), a layer having a thermal conductivity lower than that of the cured product (D) of the thermally conductive curable liquid resin composition is disposed around the first heating element (B).
2)如1)中記載之散熱結構體，其進而具有(E)電磁波屏蔽殼體。 2) The heat dissipation structure according to 1), further comprising (E) an electromagnetic wave shielding case.
3)如1)或2)中記載之散熱結構體，其中導熱性硬化性液狀樹脂組合物係藉由濕氣或加熱而硬化者。 (3) The heat dissipation structure according to the item 1 or 2, wherein the thermally conductive curable liquid resin composition is cured by moisture or heat.
4)如1)至3)中任一項所記載之散熱結構體，其中導熱性硬化性液狀樹脂組合物係包含(I)硬化性丙烯酸系樹脂或硬化性聚環氧丙烷系樹脂以及(II)導熱性填充材料者，其黏度為30Pa‧s以上且3000Pa‧s以下，導熱率為0.5W/(m‧K)以上。 The heat-dissipating structure according to any one of the above-mentioned, wherein the thermally conductive curable liquid resin composition comprises (I) a curable acrylic resin or a curable polypropylene oxide resin and II) The thermal conductive filler has a viscosity of 30 Pa ‧ or more and 3,000 Pa ‧ or less, and a thermal conductivity of 0.5 W/(m ‧ K) or more.
5)如2)至4)中任一項所記載之散熱結構體，其中電磁波屏蔽殼體(E)設置於第2面上，導熱性硬化性液狀樹脂組合物之硬化物(D)配置於第2面上所設置之該電磁波屏蔽殼體(E)內。 (5) The heat dissipation structure according to any one of the items 2 to 4, wherein the electromagnetic wave shielding case (E) is provided on the second surface, and the cured (D) of the thermally conductive liquid resin composition is disposed. The electromagnetic wave shielding case (E) provided on the second surface.
6)如2)至5)中任一項所記載之散熱結構體，其中於自與印刷基板(A)之第1面垂直之方向透視之情形時，配置第1發熱體(B)之區域之至少一部分與配置第2發熱體(C)及導熱性硬化性液狀樹脂組合物之硬化物(D)之區域之至少一部分重疊。 (6) The heat dissipation structure according to any one of the items 2 to 5, wherein the first heat generating body (B) is disposed in a direction perpendicular to a direction perpendicular to the first surface of the printed circuit board (A) At least a part of the region overlaps with at least a portion of the region where the cured material (D) of the second heat generating body (C) and the thermally conductive curable liquid resin composition is disposed.
本發明之散熱結構體藉由使自配置於印刷基板之兩面的電子零件所產生之熱通過配置於第2面之導熱性硬化性液狀樹脂組合物之硬化物放熱，而控制熱之傳導方向，從而可防止第1面上之電子零件之過熱，防止電子零件之性能劣化。 The heat dissipating structure of the present invention controls the heat conduction direction by radiating heat generated from the electronic components disposed on both surfaces of the printed substrate through the cured material of the thermally conductive curable liquid resin composition disposed on the second surface. Therefore, overheating of the electronic components on the first surface can be prevented, and the performance of the electronic components can be prevented from deteriorating.
11、11a、11b‧‧‧電磁波屏蔽殼體 11, 11a, 11b‧‧‧ electromagnetic shielding shell
12‧‧‧印刷基板 12‧‧‧Printed substrate
13、13a、13b、13c、13d‧‧‧電子零件(發熱體) 13, 13a, 13b, 13c, 13d‧‧‧ Electronic parts (heating elements)
14‧‧‧發熱體之周圍(亦可配置導熱性硬化性液狀樹脂組合物之硬化物的空間) 14‧‧‧War around the heating element (the space of the hardened material of the thermally conductive liquid resin composition may be disposed)
15‧‧‧導熱性硬化性液狀樹脂組合物之硬化物 15‧‧‧The cured product of the thermally conductive curable liquid resin composition
圖1係表示本發明之散熱結構體之印刷基板、電磁波屏蔽殼體及發熱體之配置之一例的概略剖面圖。 1 is a schematic cross-sectional view showing an example of arrangement of a printed circuit board, an electromagnetic wave shielding case, and a heat generating body of the heat dissipation structure of the present invention.
圖2係表示本發明之散熱結構體之印刷基板及發熱體之配置之一例的概略剖面圖。 2 is a schematic cross-sectional view showing an example of arrangement of a printed circuit board and a heat generating body of the heat dissipation structure of the present invention.
圖3係關於本發明之比較例的概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing a comparative example of the present invention.
圖4係關於本發明之實施例的概略俯視圖。 Figure 4 is a schematic plan view of an embodiment of the present invention.
圖5係關於本發明之比較例的概略剖面圖。 Fig. 5 is a schematic cross-sectional view showing a comparative example of the present invention.
圖6係關於本發明之實施例的概略剖面圖。 Figure 6 is a schematic cross-sectional view of an embodiment of the present invention.
圖7係表示本發明之散熱結構體之一例的概略剖面圖。 Fig. 7 is a schematic cross-sectional view showing an example of a heat dissipation structure of the present invention.
本發明之散熱結構體之特徵在於：其係具有(A)印刷基板、(B)第1發熱體、(C)第2發熱體以及(D)導熱性硬化性液狀樹脂組合物之硬化物者，印刷基板(A)具有第1面及位於第1面之相反側的第2面，第1發熱體(B)配置於第1面上，第2發熱體(C)配置於第2面上，第1發熱體(B)之發熱量為第2發熱體(C)之發熱量以上，於第2發熱體(C)之周圍配置導熱性硬化性液狀樹脂組合物之硬化物(D)，於第1發熱體(B)之周圍配置導熱率低於導熱性硬化性液狀樹脂組合物之硬化物(D)的層。 The heat dissipation structure of the present invention is characterized by comprising (A) a printed substrate, (B) a first heat generating body, (C) a second heat generating body, and (D) a cured product of a thermally conductive curable liquid resin composition. The printed circuit board (A) has a first surface and a second surface located on the opposite side of the first surface. The first heating element (B) is disposed on the first surface, and the second heating element (C) is disposed on the second surface. In the first heat generating element (C), the heat generation amount of the heat generating curable liquid resin composition is placed around the second heat generating element (C). A layer having a thermal conductivity lower than that of the cured product (D) of the thermally conductive curable liquid resin composition is disposed around the first heating element (B).
再者，於本說明書中，導熱性硬化性液狀樹脂組合物之硬化物亦稱為導熱性硬化物。 In the present specification, the cured product of the thermally conductive curable liquid resin composition is also referred to as a thermally conductive cured product.
又，印刷基板之第1面亦稱為印刷基板之正面側，第2面亦稱為 印刷基板之背面側。 Moreover, the first surface of the printed substrate is also referred to as the front side of the printed substrate, and the second surface is also referred to as The back side of the printed substrate.
本發明之散熱結構體係如下者：於兩面配置有發熱體之印刷基板中，在期望進一步散熱之發熱體之相反側之面所配置的發熱體之周圍配置導熱性硬化物。 In the heat dissipation structure system of the present invention, in the printed circuit board on which the heat generating body is disposed on both sides, a heat conductive cured material is disposed around the heat generating body disposed on the surface opposite to the heat generating body that is expected to further dissipate heat.
配置於第1發熱體之周圍的層就於印刷基板之背面側散熱之觀點而言，必需為導熱率低於導熱性硬化性液狀樹脂組合物之硬化物(D)者。導熱率較佳為未達0.5W/(m‧K)，更佳為未達0.4W/(m‧K)，進而較佳為未達0.3W/(m‧K)。導熱率為23℃下測定之值。作為此種層，可列舉樹脂層、樹脂以外之填充物之層、空間層(空氣等之氣體層、真空等)等。又，亦不限定於該狀態，可列舉氣體、液體、固體、真空等。更具體而言，可列舉空氣、墊片、發泡體、底部填充劑等。其中，就無需其他步驟或材料之觀點而言，較佳為空間層。亦可設置有材質或導熱率不同之複數個層。 From the viewpoint of dissipating heat on the back side of the printed circuit board, the layer disposed around the first heat generating element must have a heat conductivity lower than that of the heat curable liquid resin composition (D). The thermal conductivity is preferably less than 0.5 W/(m‧K), more preferably less than 0.4 W/(m‧K), and even more preferably less than 0.3 W/(m‧K). The thermal conductivity is a value measured at 23 °C. Examples of such a layer include a resin layer, a layer of a filler other than the resin, a space layer (a gas layer such as air, a vacuum, etc.). Further, the present invention is not limited to this state, and examples thereof include a gas, a liquid, a solid, a vacuum, and the like. More specifically, air, a gasket, a foam, an underfill, etc. are mentioned. Among them, a space layer is preferred from the viewpoint of no other steps or materials. It is also possible to provide a plurality of layers having different materials or thermal conductivity.
本發明中所使用之印刷基板係用於固定電子設備或精密設備所使用之電子零件而進行配線之電氣製品之零件，只要是藉由固定積體電路、電阻器、電容器等多數之電子零件，並於該零件間利用配線進行連接而構成電子電路者即可，並無特別限定。例如，可列舉使用無柔軟性之絕緣體機材的硬質基板、絕緣體基板使用較薄且具有柔軟性之材料的軟性基板、硬質之材料與較薄且具有柔軟性之材料複合而成的硬質軟性基板等。 The printed circuit board used in the present invention is a component for an electric product to be used for fixing an electronic component used in an electronic device or a precision device, and is used as long as it is a fixed number of electronic components such as an integrated circuit, a resistor, and a capacitor. It is not particularly limited as long as the electronic circuit is connected by wiring between the components. For example, a rigid substrate using a non-flexible insulator material, a flexible substrate using a thin and flexible material for an insulator substrate, a hard flexible material such as a hard material and a thin and flexible material may be used. .
又，作為印刷基板之材質，可列舉酚醛紙、環氧紙、玻璃‧環氧、玻璃纖維‧環氧、玻璃‧複合體、鐵氟龍(註冊商標)、陶瓷、低溫同時焙燒陶瓷、聚醯亞胺、聚酯、金屬、氟等。 Further, examples of the material of the printed substrate include phenolic paper, epoxy paper, glass, epoxy, glass fiber, epoxy, glass, composite, Teflon (registered trademark), ceramic, low-temperature simultaneous baking ceramic, and polyfluorene. Imine, polyester, metal, fluorine, and the like.
又，作為印刷基板之構造，存在僅單面存在圖案之單面基板或雙面存在圖案之雙面基板、絕緣體與圖案組合為薄餅狀之多層基板或 一層層堆起來的堆疊基板等之構造，但只要是可配置發熱體之構造即可，並無特別限定。 Further, as a structure of the printed substrate, there is a single-sided substrate having a single-sided pattern or a double-sided substrate having a pattern on both sides, a multilayer substrate having a combination of an insulator and a pattern, or The structure of a stacked substrate or the like stacked in layers is not particularly limited as long as it is a structure in which a heat generating body can be disposed.
又，亦可於印刷基板上配置配線或發熱體以外之電子零件等。 Further, an electronic component other than the wiring or the heating element may be disposed on the printed circuit board.
作為本發明所使用之發熱體(B)、(C)，可列舉電子零件，只要是於電子設備‧精密設備驅動時發熱者即可，並無特別限定。例如，可列舉電晶體、積體電路(IC)、CPU(Central Processing Unit，中央處理單元)、二極體、LED等半導體元件、電子管、電動馬達、電阻器、電容器(capacitor)、線圈、繼電器、壓電元件、轉換器、揚聲器、加熱器、各種電池、各種晶片零件等電子零件。 The heat generating elements (B) and (C) used in the present invention include electronic components, and are not particularly limited as long as they are heated when the electronic device and the precision device are driven. For example, a transistor, an integrated circuit (IC), a CPU (Central Processing Unit), a diode, a semiconductor element such as a diode, an electron tube, an electric motor, a resistor, a capacitor, a coil, and a relay can be cited. Electronic components such as piezoelectric elements, converters, speakers, heaters, various batteries, and various wafer parts.
本發明中所使用之發熱體係指發熱密度為0.2W/cm2以上者。若發熱密度為0.2W/cm2以上，則於驅動時發熱直至高溫，容易產生零件之性能下降，故可充分地發揮本發明之效果。發熱密度較佳為0.5W/cm2以上。又，發熱密度較佳為1000W/cm2以下，更佳為800W/cm2以下。再者，所謂發熱密度，係指於單位時間自單位面積釋放出之熱能。 The heat generating system used in the present invention means a heat generating density of 0.2 W/cm 2 or more. When the heat generation density is 0.2 W/cm 2 or more, heat is generated up to a high temperature during driving, and the performance of the component is likely to be deteriorated, so that the effects of the present invention can be sufficiently exhibited. The heat generation density is preferably 0.5 W/cm 2 or more. Further, the heat generation density is preferably 1000 W/cm 2 or less, more preferably 800 W/cm 2 or less. In addition, the heat density refers to heat energy released from a unit area per unit time.
發熱體於同一面上可僅有一個，亦可安裝有複數個。又，於配置電磁波屏蔽殼體之情形時，上述發熱體可僅位於電磁波屏蔽殼體內，亦可配置於電磁波屏蔽殼體之外部。關於電磁波屏蔽殼體內之發熱體，亦可於同一面上僅有一個，亦可安裝有複數個。於同一面上安裝有複數個發熱體之情形時，發熱體之距基板之高度不必一致。 The heating element may have only one on the same side, and a plurality of them may be installed. Further, when the electromagnetic wave shielding case is disposed, the heating element may be disposed only in the electromagnetic wave shielding case or may be disposed outside the electromagnetic wave shielding case. Regarding the heating element in the electromagnetic wave shielding case, there may be only one on the same surface, or a plurality of them may be mounted. When a plurality of heating elements are mounted on the same surface, the height of the heating element from the substrate does not have to be uniform.
本發明所使用之第1發熱體之發熱量為第2發熱體之發熱量以上。 The calorific value of the first heating element used in the present invention is equal to or higher than the calorific value of the second heating element.
發熱量可由發熱體之發熱密度及發熱部分之面積求出。又，於同一面配置複數個發熱體之情形時，將第1面上之各發熱體之發熱量的和作為第1發熱體之發熱量，將第2面上之各發熱體之發熱量的和作 為第2發熱體之發熱量。 The amount of heat generated can be obtained from the heat generation density of the heat generating body and the area of the heat generating portion. In the case where a plurality of heat generating bodies are disposed on the same surface, the sum of the heat generation amounts of the heat generating elements on the first surface is used as the heat generation amount of the first heat generating body, and the heat generation amount of each of the heat generating bodies on the second surface is And It is the calorific value of the second heating element.
第1發熱體之發熱量較佳為0.5W以上，更佳為0.8W以上，進而較佳為1.0W以上。又，第1發熱體之發熱量較佳為1000W以下，更佳為900W以下，進而較佳為800W以下。 The calorific value of the first heating element is preferably 0.5 W or more, more preferably 0.8 W or more, still more preferably 1.0 W or more. Further, the amount of heat generated by the first heating element is preferably 1000 W or less, more preferably 900 W or less, still more preferably 800 W or less.
第2發熱體之發熱量較佳為0.2W以上，更佳為0.5W以上，進而較佳為0.8W以上。又，第2發熱體之發熱量較佳為1000W以下，更佳為900W以下，進而較佳為800W以下。 The calorific value of the second heating element is preferably 0.2 W or more, more preferably 0.5 W or more, still more preferably 0.8 W or more. Further, the amount of heat generated by the second heating element is preferably 1000 W or less, more preferably 900 W or less, still more preferably 800 W or less.
於本發明之散熱結構體中，導熱性硬化性液狀樹脂組合物之硬化物配置於第2發熱體之周圍。 In the heat dissipation structure of the present invention, the cured product of the thermally conductive curable liquid resin composition is disposed around the second heat generator.
所謂發熱體之「周圍」，係指發熱體之附近、自發熱體產生之熱所傳導之區域。具體而言，係指構成電子設備之各種零件之表面或該零件間之區域，作為該零件，可列舉印刷基板、發熱體、電磁波屏蔽殼體、配線、銅線、銅板、發熱體以外之電子零件、石墨片材、散熱墊等。 The "surroundings" of the heating element refer to the area in the vicinity of the heating element and the heat generated by the heating element. Specifically, it refers to a surface of various components constituting an electronic device or a region between the components, and examples of the component include a printed circuit board, a heat generating body, an electromagnetic wave shielding case, wiring, a copper wire, a copper plate, and an electron other than the heating element. Parts, graphite sheets, cooling pads, etc.
就可有效地使發熱體之熱散掉，結果關係到電子設備之性能提高而言，本發明所使用之導熱性硬化性液狀樹脂組合物之硬化物之導熱率較佳為0.5W/(m‧K)以上，更佳為0.8W/(m‧K)以上，進而較佳為1.0W/(m‧K)以上。若導熱率未達0.5W/(m‧K)，則可能會產生無法較佳地散熱而使發熱體或其周邊之零件之性能劣化、壽命縮短等各種問題。 The heat of the heat generating body is effectively dissipated, and as a result, the thermal conductivity of the cured product of the thermally conductive curable liquid resin composition used in the present invention is preferably 0.5 W/(in terms of improvement in performance of the electronic device). More preferably, it is 0.8 W/(m‧K) or more, and more preferably 1.0 W/(m‧K) or more. When the thermal conductivity is less than 0.5 W/(m‧K), various problems such as deterioration of performance of the heating element or its surrounding components and shortening of the life may occur due to the inability to dissipate heat.
再者，導熱率為於23℃下測定之值。又，導熱性硬化物之導熱率與導熱性硬化性液狀樹脂組合物之導熱率大致相同。 Further, the thermal conductivity was a value measured at 23 °C. Further, the thermal conductivity of the thermally conductive cured product is substantially the same as the thermal conductivity of the thermally conductive curable liquid resin composition.
又，本發明所使用之導熱性硬化物較佳為拉伸彈性模數為50MPa以下之橡膠彈性體，進而較佳為拉伸彈性模數為40MPa以下。若拉伸彈性模數超過50MPa，則存在於產生基板之膨脹‧收縮以及來 自外部之壓力所引起之壓縮‧變形之時，無法追隨該等變化，從而樹脂產生裂痕，或零件損傷之虞。所謂拉伸彈性模數，係指基於JIS K 6251而測定之拉伸彈性模數。 Further, the thermally conductive cured product used in the present invention is preferably a rubber elastic body having a tensile modulus of 50 MPa or less, and more preferably has a tensile modulus of 40 MPa or less. If the tensile modulus of elasticity exceeds 50 MPa, there is expansion and contraction of the substrate. At the time of compression and deformation caused by external pressure, the change cannot be followed, and the resin may be cracked or the part may be damaged. The tensile elastic modulus refers to a tensile elastic modulus measured based on JIS K 6251.
作為構成拉伸彈性模數為50MPa以下之橡膠彈性體的樹脂，例如可列舉以下所說明之硬化性丙烯酸系樹脂或硬化性甲基丙烯酸系樹脂、以硬化性聚環氧丙烷系樹脂為代表之硬化性聚醚系樹脂、以硬化性聚異丁烯系樹脂為代表之硬化性聚烯烴系樹脂、聚矽氧樹脂等。 Examples of the resin constituting the rubber elastic body having a tensile modulus of 50 MPa or less include a curable acrylic resin or a curable methacrylic resin described below, and a curable polypropylene oxide resin. A curable polyether-based resin, a curable polyolefin-based resin typified by a curable polyisobutylene-based resin, a polyfluorene-based resin, or the like.
導熱性硬化物之形狀無特別限定，例示有片狀、帶狀、短條狀、圓盤狀、圓環狀、塊狀、不定形狀。 The shape of the thermally conductive cured product is not particularly limited, and examples thereof include a sheet shape, a belt shape, a short strip shape, a disk shape, an annular shape, a block shape, and an indefinite shape.
又，亦可設置有材質或導熱率不同之複數個導熱性硬化物。 Further, a plurality of thermally conductive cured materials having different materials or thermal conductivity may be provided.
配置於第2發熱體之周圍的導熱性硬化物可以完全地覆蓋該發熱體之方式配置，亦可如圖7所示以發熱體之一部分露出之方式配置。於同一面配置複數個發熱體之情形時，可完全地覆蓋全部之發熱體，可幾個發熱體露出，亦可全部發熱體露出。 The thermally conductive cured material disposed around the second heat generating body may be disposed so as to completely cover the heat generating body, and may be disposed such that one of the heat generating bodies is partially exposed as shown in FIG. 7 . When a plurality of heating elements are disposed on the same surface, all of the heating elements can be completely covered, and several heating elements can be exposed, or all of the heating elements can be exposed.
較佳為配置於第2發熱體之周圍的導熱性硬化物與該發熱體接觸。關於導熱性樹脂層與發熱體接觸之部分，較佳為導熱性樹脂層與發熱體密接。此係為了增加接觸面積而實現良好之散熱性。 Preferably, the thermally conductive cured material disposed around the second heat generating body is in contact with the heat generating body. It is preferable that the heat conductive resin layer is in close contact with the heat generating body in the portion where the heat conductive resin layer is in contact with the heat generating body. This is to achieve good heat dissipation in order to increase the contact area.
就使經由印刷基板之熱傳導變得容易之觀點而言，較佳為導熱性硬化物進而與印刷基板接觸。 From the viewpoint of facilitating heat conduction through the printed substrate, it is preferred that the thermally conductive cured material is further in contact with the printed substrate.
為了使自第1發熱體產生之熱迅速地傳導，較佳為導熱性硬化物與第1發熱體之距離較短。又，為了使自第1發熱體產生之熱迅速地傳導，較佳為於自與印刷基板之第1面垂直之方向透視之情形時，配置第1發熱體之區域之至少一部分與配置第2發熱體及導熱性硬化物之區域之至少一部分重疊。 In order to rapidly conduct heat generated from the first heat generating body, it is preferable that the distance between the thermally conductive cured product and the first heat generating body is short. Further, in order to rapidly conduct heat generated from the first heat generating body, it is preferable to arrange at least a part of the region in which the first heat generating body is disposed and to arrange the second portion when it is seen from a direction perpendicular to the first surface of the printed circuit board. At least a portion of the regions of the heating element and the thermally conductive cured material overlap.
於導熱性硬化物配置於電磁波屏蔽殼體內之情形時，亦可與電磁波屏蔽殼體之頂壁(與印刷基板對向之部分)或側壁(頂壁以外之部 分)接觸。由於可使自發熱體產生之熱向電磁波屏蔽殼體傳導，故可抑制發熱體之溫度上升，從而可大大地有助於防止性能劣化。 When the thermally conductive cured material is disposed in the electromagnetic wave shielding case, the top wall of the electromagnetic shielding case (the portion opposite to the printed substrate) or the side wall (the portion other than the top wall) may be used. Points) contact. Since the heat generated by the self-heating body can be conducted to the electromagnetic wave shielding case, the temperature rise of the heating element can be suppressed, and the performance deterioration can be greatly prevented.
由於本發明所使用之導熱性硬化性液狀樹脂組合物於硬化前為液狀物，故亦可追隨大大小小具有各種尺寸、高度之發熱體，從而密接性提高。因此，與發熱體之接觸熱阻較小，從而可高效率地使產生之熱散掉。又，於向電磁波屏蔽殼體內填充之情形時，不僅可無間隙地進行填充，而且由於硬化而無相繼之向系統外流失之擔憂。 Since the thermally conductive curable liquid resin composition used in the present invention is a liquid material before curing, it is possible to follow a large and small heat generating body having various sizes and heights, and the adhesion is improved. Therefore, the contact heat resistance with the heating element is small, so that the generated heat can be efficiently dissipated. Further, in the case of filling into the electromagnetic wave shielding case, not only the filling can be performed without a gap, but also there is no concern that it is lost to the outside of the system due to hardening.
本發明所使用之導熱性硬化性液狀樹脂組合物較佳為藉由濕氣或加熱而硬化者。 The thermally conductive curable liquid resin composition used in the present invention is preferably cured by moisture or heat.
較佳為導熱性硬化性液狀樹脂組合物含有硬化性丙烯酸系樹脂或硬化性聚環氧丙烷系樹脂(I)以及導熱性填充材料(II)。除該等以外，亦可根據需要添加用以使組成物硬化之硬化觸媒、抗熱老化劑、塑化劑、增量劑、觸變性賦予劑、貯藏穩定劑、脫水劑、偶合劑、紫外線吸收劑、阻燃劑、電磁波吸收劑、填充劑、溶劑等。 The thermally conductive curable liquid resin composition preferably contains a curable acrylic resin, a curable polypropylene oxide resin (I), and a thermally conductive filler (II). In addition to these, a curing catalyst, a heat-resistant aging agent, a plasticizer, a bulking agent, a thixotropic imparting agent, a storage stabilizer, a dehydrating agent, a coupling agent, and an ultraviolet ray for curing the composition may be added as needed. Absorbent, flame retardant, electromagnetic wave absorber, filler, solvent, and the like.
較佳為導熱性硬化性液狀樹脂組合物於硬化前之黏度為30Pa‧s以上，雖然具有流動性，但較佳為黏度相對高之液狀樹脂組合物。上述導熱性硬化性液狀樹脂組合物於硬化前之黏度更佳為40Pa‧s以上，進而較佳為50Pa‧s以上。雖然對硬化前之黏度之上限值無特別限制，但較佳為5000Pa‧s以下，更佳為4000Pa‧s以下，進而較佳為3000Pa‧s以下。若上述導熱性硬化性液狀樹脂組合物於硬化前之黏度未達30Pa‧s，則有時會產生於塗佈後流失等作業性下降之問題。若上述導熱性硬化性液狀樹脂組合物於硬化前之黏度超過5000Pa‧s，則有時會變得難以塗佈，或於塗佈時捲入空氣而成為降低導熱性之一個原因。再者，硬化前之黏度係於23℃50%RH之環境下使用BH型黏度計於2rpm之條件下所測定之值。 The heat-curable liquid resin composition preferably has a viscosity of 30 Pa ‧ or more before curing, and is preferably a liquid resin composition having a relatively high viscosity although it has fluidity. The viscosity of the thermally conductive curable liquid resin composition before curing is more preferably 40 Pa ‧ or more, and still more preferably 50 Pa ‧ s or more. Although the upper limit of the viscosity before hardening is not particularly limited, it is preferably 5,000 Pa ‧ or less, more preferably 4,000 Pa ‧ or less, and still more preferably 3,000 Pa ‧ or less. When the viscosity of the thermally conductive curable liquid resin composition before curing is less than 30 Pa ‧ s, there is a problem that workability such as loss after application is lowered. When the viscosity of the thermally conductive curable liquid resin composition before curing is more than 5,000 Pa·s, it may become difficult to apply, or air may be entrained during coating to cause a decrease in thermal conductivity. Further, the viscosity before hardening was measured at a temperature of 23 ° C and 50% RH using a BH type viscometer at 2 rpm.
導熱性硬化性液狀樹脂組合物之導熱率較佳為0.5W/(m‧K)以上，更佳為0.8W/(m‧K)以上，進而較佳為1.0W/(m‧K)以上。 The thermal conductivity of the thermally conductive curable liquid resin composition is preferably 0.5 W/(m‧K) or more, more preferably 0.8 W/(m‧K) or more, and still more preferably 1.0 W/(m ‧ K) the above.
作為硬化性丙烯酸系樹脂或硬化性聚環氧丙烷系樹脂，較佳為於分子內具有反應性基且具有硬化性之液狀樹脂。作為反應性基，可使用環氧基、水解性矽烷基、乙烯基、丙烯醯基、SiH基、胺基甲酸酯基、碳二醯亞胺基、羧酸酐基與胺基之組合等各種反應性官能基。 The curable acrylic resin or the curable polypropylene oxide resin is preferably a liquid resin having a reactive group in the molecule and having curability. As the reactive group, various kinds of epoxy groups, hydrolyzable alkylene groups, vinyl groups, acrylonitrile groups, SiH groups, urethane groups, carbodiimide groups, carboxylic anhydride groups and amine groups can be used. Reactive functional group.
於上述硬化性樹脂藉由兩種反應性基之組合或反應性基與硬化觸媒之反應而硬化之情形時，於以二液型組成物之形式準備之後，於向基板或發熱體塗佈之時，可藉由混合二液而使其硬化。於具有水解性矽烷基之硬化性樹脂之情形時，由於可與空氣中之濕氣進行反應而硬化，故亦可製成一液型室溫硬化性組成物。於乙烯基與SiH基與Pt觸媒之組合之情形、或自由基起始劑與丙烯醯基之組合等之情形時，於製成一液型硬化性組成物或二液型硬化性組成物之後，亦可藉由加熱直至交聯溫度，或賦予紫外線或電子束等之交聯能量而使其硬化。一般而言，於對散熱結構體整體進行一定程度之加熱較為容易之情形時，較佳為使用加熱硬化型組成物，於散熱結構體之加熱較為困難之情形時，較佳為製成二液型硬化性組成物，或製成濕氣硬化型組成物，但並不限定於該等。 When the curable resin is cured by a combination of two kinds of reactive groups or a reaction between a reactive group and a curing catalyst, after being prepared in the form of a two-liquid type composition, it is applied to a substrate or a heating element. At this time, it can be hardened by mixing the two liquids. In the case of a curable resin having a hydrolyzable alkylene group, it can be cured by reacting with moisture in the air, so that it can be formed into a one-pack type room temperature curable composition. In the case of a combination of a vinyl group and a SiH group and a Pt catalyst, or a combination of a radical initiator and an acrylonitrile group, a one-liquid type hardening composition or a two-liquid type hardening composition is produced. Thereafter, it may be cured by heating to a crosslinking temperature or by imparting crosslinking energy such as ultraviolet rays or electron beams. In general, when it is easy to heat the entire heat dissipation structure to a certain extent, it is preferable to use a heat-curing composition. When the heat dissipation structure is difficult to heat, it is preferably made into a two-liquid solution. The type hardening composition or the moisture curing type composition is not limited thereto.
就低分子量矽氧烷所引起之電子設備內污染之問題較少、或耐熱性優異等而言，較佳為硬化性丙烯酸系樹脂或硬化性聚環氧丙烷系樹脂。作為硬化性丙烯酸系樹脂，可使用公知之各種反應性丙烯酸樹脂。於該等之中，較佳為使用於分子末端具有反應性基之丙烯酸系低聚物。作為該等硬化性丙烯酸系樹脂，最佳可使用利用活性自由基聚合尤其是利用原子移動自由基聚合製造而成之硬化性丙烯酸系樹脂與硬化觸媒之組合。作為此種樹脂之例，已知有日本Kaneka股份有限公 司製造之Kaneka XMAP。又，作為硬化性聚環氧丙烷系樹脂，可使用公知之各種反應性聚環氧丙烷樹脂，例如可列舉日本Kaneka股份有限公司製造之Kaneka MS Polymer。該等硬化性液狀樹脂可單獨使用，亦可併用兩種以上而使用。 A curable acrylic resin or a curable polypropylene oxide resin is preferable because the problem of contamination in the electronic device caused by the low molecular weight siloxane is small, or the heat resistance is excellent. As the curable acrylic resin, various known reactive acrylic resins can be used. Among these, an acrylic oligomer having a reactive group at a molecular terminal is preferably used. As the curable acrylic resin, a combination of a curable acrylic resin and a curing catalyst which are produced by living radical polymerization, in particular, by atomic mobile radical polymerization can be preferably used. As an example of such a resin, Kaneka Co., Ltd. of Japan is known. Kaneka XMAP manufactured by the company. Further, as the curable polypropylene oxide-based resin, various known reactive polypropylene oxide resins can be used, and for example, Kaneka MS Polymer manufactured by Kaneka Co., Ltd., Japan can be used. These curable liquid resins may be used singly or in combination of two or more.
作為導熱性填充材料(II)，就導熱率、獲取性、可賦予絕緣性或電磁波吸收性等電氣特性、填充性、毒性等各種觀點而言，可較佳列舉石墨、金剛石等碳化合物；氧化鋁、氧化鎂、氧化鈹、氧化鈦、氧化鋯、氧化鋅等金屬氧化物；氮化硼、氮化鋁、氮化矽等金屬氮化物；碳化硼、碳化鋁、碳化矽等金屬碳化物；氫氧化鋁、氫氧化鎂等金屬氫氧化物；碳酸鎂、碳酸鈣等金屬碳酸鹽；結晶性氧化矽；丙烯腈系聚合物焙燒物、呋喃樹脂焙燒物、苯甲酚樹脂焙燒物、聚氯乙烯焙燒物、砂糖之焙燒物、木炭之焙燒物等有機性聚合物焙燒物；與Zn鐵氧體之複合鐵氧體；Fe-Al-Si系三元合金；金屬粉末等。 The heat conductive filler (II) is preferably a carbon compound such as graphite or diamond in terms of thermal conductivity, availability, electrical properties such as insulation properties and electromagnetic wave absorbability, filling properties, and toxicity. a metal oxide such as aluminum, magnesium oxide, cerium oxide, titanium oxide, zirconium oxide or zinc oxide; a metal nitride such as boron nitride, aluminum nitride or cerium nitride; a metal carbide such as boron carbide, aluminum carbide or lanthanum carbide; Metal hydroxide such as aluminum hydroxide or magnesium hydroxide; metal carbonate such as magnesium carbonate or calcium carbonate; crystalline cerium oxide; acrylonitrile-based polymer calcined product, furan resin calcined product, cresol resin calcined product, polychlorinated chlorine An organic polymer calcined product such as an ethylene calcined product, a calcined material of granulated sugar, or a calcined product of charcoal; a composite ferrite with Zn ferrite; a Fe-Al-Si ternary alloy; a metal powder.
又，就提高對於樹脂之分散性之方面而言，該等導熱性填充材料較佳為利用矽烷偶合劑(乙烯基矽烷、環氧矽烷、(甲基)丙烯酸矽烷、異氰酸酯矽烷、氯矽烷、胺基矽烷等)或鈦酸酯偶合劑(鈦酸烷氧酯、鈦酸胺酯等)，或脂肪酸(己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、山萮酸等飽和脂肪酸，山梨酸、反油酸、油酸、亞麻油酸、次亞麻油酸、芥酸等不飽和脂肪酸等)或樹脂酸(松香酸、海松脂酸、左旋海松脂酸、新松香酸(neoabietic acid)、長葉松酸、脫氫松香酸、異海松脂酸、山達海松脂酸、Colm酸(Colm acid)、開環脫氫松香酸、二氫松脂酸等)等進行表面處理者。 Further, in terms of improving the dispersibility of the resin, the thermally conductive filler is preferably a decane coupling agent (vinyl decane, epoxy decane, (meth) decane, isocyanate decane, chlorodecane, amine Base oxime, etc.) or titanate coupling agent (alkoxylate, titanate, etc.), or fatty acid (hexanoic acid, caprylic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, mountain Saturated fatty acids such as citric acid, sorbic acid, oleic acid, oleic acid, linoleic acid, linoleic acid, erucic acid and other unsaturated fatty acids, etc. or resin acids (rosin acid, sea rosin acid, levofloxacin, new Neoabietic acid, long-leafed acid, dehydroabietic acid, isopimaric acid, savannah acid, Colmic acid, ring-opened dehydroabietic acid, dihydroabietic acid, etc. Surface processor.
作為此種導熱性填充材料之使用量，就可提高自導熱性硬化性液狀樹脂組合物獲得之硬化物之導熱率之方面而言，較佳為導熱性填充材料之體積率(%)成為全部組成物中之25容量%以上。於上述導熱 性填充材料之體積率(%)少於25容量%之情形時，存在導熱性會變得不充分之傾向。於期望導熱率進而高之情形時，更佳為將導熱性填充材料之使用量設為全部組成物中之30容量%以上，進而較佳為設為40容量%以上，尤佳為設為50容量%以上。又，較佳為導熱性填充材料之體積率(%)成為全部組成物中之90容量%以下。於上述導熱性填充材料之體積率(%)多於90容量%之情形時，硬化前之導熱性硬化性液狀樹脂組合物之黏度有時會變得過高。 The amount of use of the thermally conductive filler can be increased, and the volume fraction (%) of the thermally conductive filler is preferably increased in terms of the thermal conductivity of the cured product obtained from the thermally conductive curable liquid resin composition. 25 wt% or more of all the compositions. In the above heat conduction When the volume fraction (%) of the filler is less than 25% by volume, the thermal conductivity tends to be insufficient. When it is desired that the thermal conductivity is further high, it is more preferable to use the amount of the thermally conductive filler as 30% by volume or more of the total composition, more preferably 40% by volume or more, and even more preferably 50%. More than % capacity. Moreover, it is preferable that the volume ratio (%) of the heat conductive filler is 90% by volume or less of the total composition. When the volume fraction (%) of the thermally conductive filler is more than 90% by volume, the viscosity of the thermally conductive curable liquid resin composition before curing may become too high.
此處所謂導熱性填充材料之體積率(%)，係由樹脂成分及導熱性填充材料之各者之重量分率及比重而算出者，利用下式求出。再者，於下式中，導熱性填充材料僅記為「填充材料」。 Here, the volume fraction (%) of the thermally conductive filler is calculated from the weight fraction and specific gravity of each of the resin component and the thermally conductive filler, and is obtained by the following formula. Further, in the following formula, the thermally conductive filler is simply referred to as "filler".
填充材料體積率(容量%)=(填充材料重量比率/填充材料比重)÷[(樹脂成分重量比率/樹脂成分比重)+(填充材料重量比率/填充材料比重)]×100 Filling material volume fraction (% by volume) = (filler weight ratio / filler specific gravity) ÷ [(resin component weight ratio / resin component specific gravity) + (filler weight ratio / filler specific gravity)] × 100
此處，所謂樹脂成分，係指除導熱性填充材料以外之全部成分。 Here, the resin component means all components other than the thermal conductive filler.
又，作為提高導熱性填充材料對於樹脂之填充率的一種方法，適合併用兩種以上粒徑不同之導熱性填充材料。於此情形時，較佳為將粒徑較大之導熱性填充材料之粒徑設為超過10μm者，將粒徑較小之導熱性填充材料之粒徑設為10μm以下。 Moreover, as one method of improving the filling rate of the thermally conductive filler to the resin, it is suitable to use two or more types of thermally conductive fillers having different particle diameters. In this case, it is preferable to set the particle diameter of the thermally conductive filler having a large particle diameter to more than 10 μm, and to set the particle diameter of the thermally conductive filler having a small particle diameter to 10 μm or less.
導熱性填充材料不僅為單獨之導熱性填充材料，亦可併用種類不同之兩種以上。 The thermal conductive filler is not limited to a single thermal conductive filler, and may be used in combination of two or more kinds.
本發明之散熱結構體亦可具有電磁波屏蔽殼體。所謂電磁波屏蔽殼體，係指藉由反射、傳導或吸收電磁波而發揮電磁波屏蔽性能之殼體。 The heat dissipation structure of the present invention may also have an electromagnetic wave shielding case. The electromagnetic wave shielding case refers to a case that exhibits electromagnetic wave shielding performance by reflecting, conducting, or absorbing electromagnetic waves.
作為電磁波屏蔽殼體(E)之材料，只要是藉由反射、傳導或吸收 電磁波而發揮電磁波屏蔽性能之材料即可，並無特別限定。例如，可使用金屬材料或塑膠材料、各種磁性材料等，其中，較佳為使用金屬材料。 As the material of the electromagnetic wave shielding case (E), as long as it is reflected, conducted or absorbed The material that exhibits electromagnetic wave shielding performance by electromagnetic waves is not particularly limited. For example, a metal material or a plastic material, various magnetic materials, or the like can be used, and among them, a metal material is preferably used.
作為金屬材料，較佳為僅由金屬元素構成之金屬材料。作為由金屬元素單體構成之金屬材料中之金屬元素，例如可列舉鋰、鈉、鉀、銣、銫等週期表1族元素；鎂、鈣、鍶、鋇等週期表2族元素；鈧、釔、鑭系元素(鑭、鈰等)、錒系元素(錒等)等週期表3族元素；鈦、鋯、鉿等週期表4族元素；釩、鈮、鉭等週期表5族元素；鉻、鉬、鎢等週期表6族元素；錳、鎝、錸等週期表7族元素；鐵、釕、鋨等週期表8族元素；鈷、銠、銥等週期表9族元素；鎳、鈀、鉑等週期表10族元素；銅、銀、金等週期表11族元素；鋅、鎘、汞等週期表12族元素；鋁、鎵、銦、鉈等週期表13族元素；錫、鉛等週期表14族元素；銻、鉍等週期表15族元素等。 As the metal material, a metal material composed only of a metal element is preferable. Examples of the metal element in the metal material composed of the metal element monomer include a group 1 element of the periodic table such as lithium, sodium, potassium, rubidium or cesium; and a group 2 element of the periodic table such as magnesium, calcium, barium or strontium;钇, lanthanides (镧, 铈, etc.), lanthanides (锕, etc.) and other periodic table 3 elements; titanium, zirconium, hafnium and other periodic table 4 elements; vanadium, niobium, tantalum and other periodic table 5 elements; Chromium, molybdenum, tungsten and other elements of the periodic table 6; manganese, strontium, barium and other periodic table 7 elements; iron, strontium, barium and other periodic table 8 elements; cobalt, antimony, bismuth and other periodic table 9 elements; nickel, Group 10 elements of periodic table such as palladium and platinum; elements of group 11 of periodic table such as copper, silver and gold; elements of group 12 of periodic table such as zinc, cadmium and mercury; elements of group 13 of periodic table such as aluminum, gallium, indium and antimony; tin, Lead group 14 elements such as the periodic table; 15, 铋 and other elements of the 15th group of the periodic table.
另一方面，作為合金，例如可列舉不鏽鋼、銅-鎳合金、黃銅、鎳-鉻合金、鐵-鎳合金、鋅-鎳合金、金-銅合金、錫-鉛合金、銀-錫-鉛合金、鎳-鉻-鐵合金、銅-錳-鎳合金、鎳-錳-鐵合金等。 On the other hand, examples of the alloy include stainless steel, copper-nickel alloy, brass, nickel-chromium alloy, iron-nickel alloy, zinc-nickel alloy, gold-copper alloy, tin-lead alloy, and silver-tin-lead. Alloy, nickel-chromium-iron alloy, copper-manganese-nickel alloy, nickel-manganese-iron alloy, and the like.
又，作為連同金屬元素一起含有非金屬元素之各種金屬系化合物，只要是含有上述所例示之金屬元素或合金之可發揮電磁波屏蔽性能之金屬系化合物即可，並無特別限制，例如可列舉硫化銅等金屬硫化物；氧化鐵、氧化鈦、氧化錫、氧化銦、氧化鎘錫等金屬氧化物或金屬複合氧化物等。 In addition, the metal-based compound which contains a non-metal element together with a metal element is not particularly limited as long as it is a metal-based compound which exhibits electromagnetic wave shielding performance by the metal element or alloy exemplified above, and examples thereof include, for example, vulcanization. A metal sulfide such as copper; a metal oxide such as iron oxide, titanium oxide, tin oxide, indium oxide or cadmium tin oxide; or a metal composite oxide.
於上述金屬材料之中，可較佳地使用金、銀、鋁、鐵、銅、鎳、不鏽鋼、銅-鎳合金。 Among the above metal materials, gold, silver, aluminum, iron, copper, nickel, stainless steel, and copper-nickel alloy can be preferably used.
作為塑膠材料，例如可列舉聚乙炔、聚吡咯、多并苯、聚苯、聚苯胺、聚噻吩等導電性塑膠。進而可列舉石墨等碳材料。 Examples of the plastic material include conductive plastics such as polyacetylene, polypyrrole, polyacene, polyphenylene, polyaniline, and polythiophene. Further, a carbon material such as graphite can be cited.
作為磁性材料，例如可列舉軟磁性粉、各種鐵氧體、氧化鋅鬚 晶等，較佳為顯示鐵磁性或亞鐵磁性之強磁性體。具體而言，例如可列舉高透磁率鐵氧體、純鐵、含有矽原子之鐵、鎳-鐵系合金、鐵-鈷系合金、非晶質金屬高透磁率材料、鐵-鋁-矽合金、鐵-鋁-矽-鎳合金、鐵-鉻-鈷合金等。 Examples of the magnetic material include soft magnetic powder, various ferrites, and zinc oxide whiskers. A crystal or the like is preferably a ferromagnetic material exhibiting ferromagnetism or ferrimagnetism. Specific examples thereof include high magnetic permeability ferrite, pure iron, iron containing niobium atoms, nickel-iron alloy, iron-cobalt alloy, amorphous metal high magnetic permeability material, and iron-aluminum-niobium alloy. , iron-aluminum-niobium-nickel alloy, iron-chromium-cobalt alloy, and the like.
電磁波屏蔽殼體之構造只要是可發揮電磁波屏蔽性能之構造即可，並無特別限定。電磁波屏蔽殼體一般如圖1所示設置於印刷基板上之接地層，並包圍成為電磁波產生源之電子零件。一般而言，電磁波屏蔽殼體與印刷基板上之接地層係利用焊料或導電性材料等接合。電磁波屏蔽殼體亦可於不損及其電磁波屏蔽性能之範圍內開出孔或間隙。又，電磁波屏蔽殼體未必為一體物，亦可為上部可如蓋般地分離之類型或可分離為兩個以上之類型。 The structure of the electromagnetic wave shielding case is not particularly limited as long as it can exhibit electromagnetic wave shielding performance. The electromagnetic wave shielding case is generally provided on a ground layer on a printed circuit board as shown in FIG. 1, and surrounds an electronic component that serves as a source of electromagnetic waves. Generally, the electromagnetic wave shielding case and the ground layer on the printed circuit board are joined by solder or a conductive material or the like. The electromagnetic wave shielding housing can also open holes or gaps within a range that does not impair the electromagnetic wave shielding performance. Further, the electromagnetic wave shielding case is not necessarily an integral body, and may be of a type in which the upper portion may be separated like a cover or may be separated into two or more types.
電磁波屏蔽殼體可僅設置於印刷基板之第1面及第2面中之任一者，亦可設置於兩面。 The electromagnetic wave shielding case may be provided only on one of the first surface and the second surface of the printed circuit board, or may be provided on both surfaces.
發熱體(電子零件)及導熱性硬化物可配置於電磁波屏蔽殼體內，亦可配置於電磁波屏蔽殼體外。 The heating element (electronic component) and the thermally conductive cured material may be disposed in the electromagnetic wave shielding case or may be disposed outside the electromagnetic wave shielding case.
於第2面上設置有電磁波屏蔽殼體之情形時，較佳為導熱性硬化物配置於該電磁波屏蔽殼體內。其原因在於，電磁波屏蔽殼體與內部之導熱性硬化物全部成為散熱構件，從而可進行有效之散熱。 When the electromagnetic wave shielding case is provided on the second surface, it is preferable that the thermally conductive cured material is disposed in the electromagnetic wave shielding case. This is because the electromagnetic wave shield case and the heat conductive cured material inside are all made into a heat radiating member, so that heat can be efficiently dissipated.
由於電磁波屏蔽殼體越具有高導熱性，則溫度分佈變得越均勻，從而可使電磁波屏蔽殼體內之發熱體之發熱有效地向外部傳導，故而較佳。就散熱性提高之觀點而言，電磁波屏蔽殼體之導熱率較佳為1W/(m‧K)以上，更佳為3W/(m‧K)以上，進而較佳為5W/(m‧K)以上，最佳為10W/(m‧K)以上。電磁波屏蔽殼體之導熱率較佳為10000W/(m‧K)以下。 Since the electromagnetic wave shielding case has a high thermal conductivity, the temperature distribution becomes uniform, and the heat generation of the heating element in the electromagnetic wave shielding case can be efficiently conducted to the outside, which is preferable. The thermal conductivity of the electromagnetic wave shielding case is preferably 1 W/(m‧K) or more, more preferably 3 W/(m ‧ K) or more, and further preferably 5 W/(m ‧ K) from the viewpoint of improvement in heat dissipation Above, it is preferably 10 W/(m‧K) or more. The thermal conductivity of the electromagnetic wave shielding case is preferably 10,000 W/(m‧K) or less.
可使用本發明之散熱結構體來製造電子設備或精密設備。作為 電子設備‧精密設備，只要是印刷基板上具有電子零件之設備即可，並無特別限定。例如可列舉伺服器、伺服器用個人電腦、桌上型個人電腦等設備、遊戲設備、筆記型電腦、電子辭典、PDA、行動電話、智慧型手機、平板終端、可攜式音樂播放器等可攜式設備、液晶顯示器、電漿顯示器、表面傳導型電子發射元件顯示器(SED)、LED、有機EL、無機EL、液晶投影儀、鐘錶等顯示設備、噴墨印表機(噴墨頭)、電子照相裝置(顯影裝置、定影裝置、加熱輥、加熱帶)等圖像形成裝置、半導體元件、半導體組件、半導體密封殼體、半導體黏晶、CPU、記憶體、功率電晶體、功率電晶體殼體等半導體相關零件、硬質配線板、軟性配線板、陶瓷配線板、堆疊配線板、多層基板等配線基板(以上所述之配線板亦包含印刷配線板等)、真空處理裝置、半導體製造裝置、顯示設備製造裝置等製造裝置、隔熱材料、真空隔熱材料、輻射隔熱材料等隔熱裝置、DVD(光學拾取頭、雷射產生裝置、雷射受光裝置)、硬碟驅動器等資料記錄設備、相機、視訊攝影機、數位相機、數位視訊攝影機、顯微鏡、CCD(Charge Coupled Device，電荷耦合器件)等圖像記錄裝置、充電裝置、鋰離子電池、燃料電池、太陽電池等電池設備等。 The heat dissipation structure of the present invention can be used to manufacture electronic devices or precision devices. As The electronic device and the precision device are not particularly limited as long as they are devices having electronic components on a printed circuit board. For example, a server, a personal computer for a server, a desktop personal computer, a game device, a notebook computer, an electronic dictionary, a PDA, a mobile phone, a smart phone, a tablet terminal, a portable music player, etc. Portable devices such as portable devices, liquid crystal displays, plasma displays, surface conduction electron-emitting device displays (SEDs), LEDs, organic ELs, inorganic ELs, liquid crystal projectors, clocks, and inkjet printers (inkjet heads), Image forming apparatus such as an electrophotographic apparatus (developing apparatus, fixing apparatus, heating roller, heating belt), a semiconductor element, a semiconductor component, a semiconductor sealing case, a semiconductor die bond, a CPU, a memory, a power transistor, a power transistor case a wiring board such as a semiconductor-related component such as a semiconductor, a hard wiring board, a flexible wiring board, a ceramic wiring board, a stacked wiring board, or a multilayer board (the wiring board mentioned above also includes a printed wiring board, etc.), a vacuum processing apparatus, a semiconductor manufacturing apparatus, Display device manufacturing equipment such as manufacturing equipment, heat insulating materials, vacuum heat insulating materials, radiation heat insulating materials, etc., DVD (optical Image recording equipment such as pickup head, laser generating device, laser light receiving device, hard disk drive, camera, video camera, digital camera, digital video camera, microscope, CCD (Charge Coupled Device) Equipment, charging devices, lithium-ion batteries, fuel cells, solar cells and other battery equipment.
以下藉由實施例表示發明之實施態樣、效果，但本發明並不限於此。 Hereinafter, embodiments and effects of the invention will be described by way of examples, but the invention is not limited thereto.
於23℃50%RH之條件下使用BH型黏度計以2rpm測定導熱性硬化性液狀樹脂組合物之黏度。 The viscosity of the thermally conductive curable liquid resin composition was measured at 2 rpm using a BH type viscometer under conditions of 23 ° C and 50% RH.
將導熱性硬化性液狀樹脂組合物包於Saran Wrap(註冊商標)內， 使用熱盤法導熱率測定裝置TPA-501(京都電子工業股份有限公司製造)，利用以兩個試樣夾住4 尺寸之感測器的方法，於23℃下測定導熱率。 The thermally conductive curable liquid resin composition was packaged in Saran Wrap (registered trademark), and the hot plate method thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Co., Ltd.) was used to sandwich the two samples. The method of measuring the size of the sensor measures the thermal conductivity at 23 °C.
使導熱性硬化性液狀樹脂組合物於23℃、50%RH之環境下硬化而製作小啞鈴狀物，以JIS K 6251為參考測定拉伸彈性模數。 The thermally conductive curable liquid resin composition was cured in an environment of 23° C. and 50% RH to prepare a small dumbbell, and the tensile elastic modulus was measured in accordance with JIS K 6251.
製作圖3、圖4、圖5、圖6所示之簡易模型，使用被覆鐵氟龍(註冊商標)之極細熱電偶雙線TT-D-40-SLE(日本Omega Engineering公司製造)測定電子零件、基板、電磁波屏蔽殼體之各模型之溫度。再者，溫度為使電子零件模型發熱1小時之後之值。 A simple model shown in Fig. 3, Fig. 4, Fig. 5, and Fig. 6 was produced, and electronic components were measured using a very fine thermocouple double-wire TT-D-40-SLE (manufactured by Omega Engineering Co., Ltd.) coated with Teflon (registered trademark). , substrate, electromagnetic wave shielding shell temperature of each model. Furthermore, the temperature is a value after the electronic part model is heated for 1 hour.
關於各模型，電子零件(13a、13b)及電磁屏蔽殼體(11a、11b)如圖4所示分別配置於基板12之中央。熱電偶安裝於電子零件上表面及電磁屏蔽殼體上表面之各者中央以及基板之中心部。 For each model, the electronic components (13a, 13b) and the electromagnetic shielding casings (11a, 11b) are respectively disposed at the center of the substrate 12 as shown in Fig. 4 . The thermocouple is mounted on the upper surface of the upper surface of the electronic component and the upper surface of the electromagnetic shielding case and the center of the substrate.
11a、11b：電磁波屏蔽殼體‧‧‧SUS(0.3mm厚度)，20mm×20mm×1.40mm 11a, 11b: electromagnetic shielding housing ‧‧‧SUS (0.3mm thickness), 20mm×20mm×1.40mm
12：基板‧‧‧玻璃環氧製，60mm×60mm×0.75mm 12: substrate ‧ ‧ glass epoxy, 60mm × 60mm × 0.75mm
13a：電子零件(發熱體)‧‧‧氧化鋁發熱體(發熱密度為1W/cm2)、10mm×10mm×1.05mm 13a: Electronic parts (heating element) ‧ ‧ alumina heating element (heating density 1W/cm 2 ), 10mm × 10mm × 1.05mm
13b：電子零件(發熱體)‧‧‧氧化鋁發熱體(發熱密度為0.2W/cm2或0.9W/cm2)、10mm×10mm×1.05mm 13b: Electronic parts (heating element) ‧ ‧ alumina heating element (heating density is 0.2W/cm 2 or 0.9W/cm 2 ), 10mm × 10mm × 1.05mm
15：導熱性硬化物 15: Thermally conductive cured product
○記號：熱電偶安裝位置 ○ mark: thermocouple installation position
於氮氣環境下，向250L反應機添加CuBr(1.09kg)、乙腈(11.4kg)、丙烯酸丁酯(26.0kg)及2,5-二溴己二酸二乙酯(2.28kg)，於70~ 80℃下攪拌30分鐘左右。於其中添加五甲基二伸乙基三胺，開始反應。自反應開始30分鐘後起花費兩小時連續地追加丙烯酸丁酯(104kg)。反應中途適當添加五甲基二伸乙基三胺，使內溫成為70℃~90℃。至此為止所使用之五甲基二伸乙基三胺總量為220g。自反應開始起4小時後，於80℃、減壓下，藉由加熱攪拌除去揮發成分。於其中添加乙腈(45.7kg)、1,7-辛二烯(14.0kg)以及五甲基二伸乙基三胺(439g)並繼續攪拌8小時。於80℃、減壓下加熱攪拌混合物而除去揮發成分。 CuBr (1.09kg), acetonitrile (11.4kg), butyl acrylate (26.0kg) and diethyl 2,5-dibromoadipate (2.28kg) were added to the 250L reactor under nitrogen atmosphere. Stir at 80 ° C for about 30 minutes. The reaction was started by adding pentamethyldiethylethylamine. From the 30 minutes after the start of the reaction, butyl acrylate (104 kg) was continuously added for two hours. In the middle of the reaction, pentamethyldiethylethylamine was appropriately added to adjust the internal temperature to 70 ° C to 90 ° C. The total amount of pentamethyldiethyltriamine used so far was 220 g. Four hours after the start of the reaction, the volatile component was removed by heating and stirring at 80 ° C under reduced pressure. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg) and pentamethyldiethylidenetriamine (439 g) were added thereto and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C under reduced pressure to remove volatile components.
於該濃縮物中添加甲苯，於聚合物溶解之後，添加作為過濾助劑之矽藻土、作為吸附劑之矽酸鋁、水滑石，於氧氮混合氣體之環境下(氧濃度為6%)以內溫100℃進行加熱攪拌。利用過濾除去混合液中之固形物成分，於減壓下以內溫100℃加熱攪拌濾液而除去揮發成分。 Toluene is added to the concentrate, and after the polymer is dissolved, diatomaceous earth as a filter aid, aluminum citrate or hydrotalcite as an adsorbent is added, and the oxygen-nitrogen mixed gas atmosphere (oxygen concentration is 6%) is added. The mixture was heated and stirred at an internal temperature of 100 °C. The solid content in the mixed liquid was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C under reduced pressure to remove volatile components.
進而於該濃縮物中添加作為吸附劑之矽酸鋁、水滑石、抗熱劣化劑，於減壓下進行加熱攪拌(平均溫度約175℃，減壓度為10Torr以下)。 Further, aluminum citrate, hydrotalcite, and a heat deterioration inhibitor which are adsorbents are added to the concentrate, and the mixture is heated and stirred under reduced pressure (average temperature: about 175 ° C, and pressure reduction is 10 Torr or less).
進而追加作為吸附劑之矽酸鋁、水滑石，並添加抗氧化劑，於氧氮混合氣體之環境下(氧濃度為6%)以內溫150℃進行加熱攪拌。 Further, aluminum citrate or hydrotalcite as an adsorbent was added, and an antioxidant was added thereto, and the mixture was heated and stirred at an internal temperature of 150 ° C in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration: 6%).
於該濃縮物中添加甲苯，於聚合物溶解之後，利用過濾除去混合液中之固形物成分，於減壓下加熱攪拌濾液而除去揮發成分，從而獲得具有烯基之聚合物。 Toluene was added to the concentrate, and after the polymer was dissolved, the solid content in the mixed liquid was removed by filtration, and the filtrate was heated and stirred under reduced pressure to remove volatile components, thereby obtaining a polymer having an alkenyl group.
混合該具有烯基之聚合物、二甲氧基甲基矽烷(相對於烯基為2.0莫耳當量)、原甲酸甲酯(相對於烯基為1.0莫耳當量)、鉑觸媒[雙(1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷)鉑錯合物觸媒之二甲苯溶液：以下稱為鉑觸媒](以鉑計相對於聚合物1kg為10mg)，於氮氣環境下以100℃進行加熱攪拌。確認烯基消失，濃縮反應混合物而獲得末端具 有二甲氧基矽烷基之聚(丙烯酸正丁酯)樹脂(I-1)。獲得之樹脂之數量平均分子量為約26,000、分子量分佈為1.3。藉由1H NMR(Nuclear Magnetic Resonance，核磁共振)分析求出樹脂每一分子中所導入之平均矽烷基數，結果為約1.8個。 Mixing the alkenyl group-containing polymer, dimethoxymethyl decane (2.0 molar equivalents relative to the alkenyl group), methyl orthoformate (1.0 molar equivalents relative to the alkenyl group), platinum catalyst [double ( a 1,3-divinyl-1,1,3,3-tetramethyldioxane) platinum complex catalyst xylene solution: hereinafter referred to as platinum catalyst] (as opposed to polymer in terms of platinum 1 kg was 10 mg), and the mixture was heated and stirred at 100 ° C under a nitrogen atmosphere. It was confirmed that the alkenyl group disappeared, and the reaction mixture was concentrated to obtain a terminal Poly(n-butyl acrylate) resin (I-1) having dimethoxyalkylene group. The obtained resin had a number average molecular weight of about 26,000 and a molecular weight distribution of 1.3. The average number of decyl groups introduced per molecule of the resin was determined by 1H NMR (Nuclear Magnetic Resonance) analysis and found to be about 1.8.
將數量平均分子量為約2,000之聚氧化丙烯二醇作為起始劑，利用六氰合鈷酸鋅乙二醇二甲醚錯合物觸媒進行環氧丙烷之聚合，從而獲得數量平均分子量為25,500(使用日本Tosoh股份有限公司製造之HLC-8120 GPC作為送液系統，色譜柱使用日本Tosoh股份有限公司製造之TSK-GEL H型，溶媒使用THF(tetrahydrofuran，四氫呋喃)而測定之聚苯乙烯換算值)之聚環氧丙烷。繼而，添加相對於該羥基末端聚環氧丙烷之經基為1.2倍當量之NaOMe甲醇溶液而蒸餾去除甲醇，進而添加氯化烯丙基而將末端之羥基轉化為烯丙基。藉由減壓去揮發而除去未反應之氯化烯丙基。於相對於獲得之未精製之烯丙基末端聚環氧丙烷100重量份，混合正己烷300重量份、水300重量份並攪拌之後，藉由離心分離除去水，於獲得之己烷溶液中進而混合水300重量份並攪拌，於藉由再次離心分離而除去水之後，藉由減壓去揮發除去己烷。藉由以上之方法獲得末端為烯丙基之數量平均分子量為約25,500之2官能聚環氧丙烷。 A polyoxypropylene propylene having a number average molecular weight of about 2,000 is used as a starter, and propylene oxide is polymerized using a zinc hexacyanocobaltate dimethyl dimethyl ether complex catalyst to obtain a number average molecular weight of 25,500. (HLC-8120 GPC manufactured by Tosoh Co., Ltd., Japan was used as a liquid feeding system, and the column was a TSK-GEL H type manufactured by Tosoh Co., Ltd., Japan, and the solvent was measured using THF (tetrahydrofuran, tetrahydrofuran). Polypropylene oxide. Then, methanol was distilled off by adding 1.2 times equivalent of a NaOMe methanol solution to the hydroxyl group-terminated polypropylene oxide, and then an allyl chloride was added to convert the terminal hydroxyl group into an allyl group. The unreacted allyl chloride was removed by evaporation under reduced pressure. After mixing 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unrefined allyl-terminated polypropylene oxide, and stirring, water is removed by centrifugation, and the obtained hexane solution is further 300 parts by weight of water was mixed and stirred, and after removing water by centrifugation again, hexane was removed by volatilization under reduced pressure. A bifunctional polypropylene oxide having a number average molecular weight of about 25,500 having an allyl group at the end was obtained by the above method.
相對於獲得之烯丙基末端聚環氧丙烷100重量份，添加鉑含量為3wt%之鉑乙烯基矽氧烷錯合物異丙醇溶液150ppm作為觸媒，使其與三甲氧基矽烷0.95重量份於90℃下反應5小時，從而獲得三甲氧基矽烷基末端聚氧化丙烯系聚合物(I-2)。與上述同樣地，1H NMR之測定之結果為，關於末端之三甲氧基矽烷基，每一分子平均為1.3個。 With respect to 100 parts by weight of the obtained allyl-terminated polypropylene oxide, 150 ppm of a platinum vinyl alkane complex isopropyl alcohol solution having a platinum content of 3 wt% was added as a catalyst to make it and 0.90 by weight of trimethoxydecane. The mixture was reacted at 90 ° C for 5 hours to obtain a trimethoxydecyl-terminated polyoxypropylene-based polymer (I-2). As a result of the measurement by 1H NMR, the terminal trimethoxydecyl group had an average of 1.3 per molecule.
於用手充分攪拌混練合成例1中獲得之樹脂(I-1)：90重量份、合 成例2中獲得之樹脂(I-2)：10重量份、塑化劑(Monocizer W-7010，日本DIC股份有限公司製造)：100重量份、抗氧化劑(Irganox 1010)：1重量份、及導熱性填充材料(氫氧化鋁450重量份及氧化鋅100重量份)之後，一面使用5L蝶形攪拌機進行加熱混練，一面抽真空、脫水。於脫水完成後進行冷卻，混合脫水劑(A171)：2重量份、硬化觸媒(新癸酸錫、新癸酸)：各4重量份，從而獲得導熱性硬化性液狀樹脂組合物。於測定獲得之導熱性硬化性液狀樹脂組合物之黏度及導熱率之後，與圖6之簡易模型圖同樣地填充導熱性硬化性液狀樹脂組合物而製作散熱結構體。於其後評價溫度。將結果示於表1中。 The resin (I-1) obtained in Synthesis Example 1 was kneaded thoroughly by hand: 90 parts by weight, combined Resin (I-2) obtained in Example 2: 10 parts by weight, a plasticizer (Monocizer W-7010, manufactured by Nippon DIC Co., Ltd.): 100 parts by weight, an antioxidant (Irganox 1010): 1 part by weight, and After the thermal conductive filler (450 parts by weight of aluminum hydroxide and 100 parts by weight of zinc oxide), the mixture was heated and kneaded using a 5 L butterfly stirrer, and vacuumed and dehydrated. After the completion of the dehydration, the mixture was cooled, and the dehydrating agent (A171) was mixed: 2 parts by weight, and a curing catalyst (tin neodecanoate or neodecanoic acid): 4 parts by weight each to obtain a thermally conductive curable liquid resin composition. After measuring the viscosity and thermal conductivity of the thermally conductive curable liquid resin composition obtained, the thermally conductive curable liquid resin composition was filled in the same manner as in the simple model diagram of FIG. 6 to produce a heat dissipation structure. The temperature was evaluated thereafter. The results are shown in Table 1.
再者，導熱性硬化性液狀樹脂組合物之黏度為350~400Pa‧s，導熱率為1.1W/(m‧K)。硬化物之拉伸彈性模數為2.0MPa。 Further, the thermally conductive curable liquid resin composition has a viscosity of 350 to 400 Pa s and a thermal conductivity of 1.1 W/(m ‧ K). The tensile modulus of the cured product was 2.0 MPa.
於不使用導熱性硬化性液狀樹脂組合物之情況下與實施例1、2同樣地進行評價。將評價結果示於表1中。 The evaluation was carried out in the same manner as in Examples 1 and 2 except that the thermally conductive curable liquid resin composition was not used. The evaluation results are shown in Table 1.
與圖3之簡易模型圖同樣地填充導熱性硬化性液狀樹脂組合物，與實施例1、2同樣地製作散熱結構體並進行評價。將評價結果示於表1中。 The thermally conductive curable liquid resin composition was filled in the same manner as in the simple model diagram of FIG. 3, and a heat dissipation structure was produced and evaluated in the same manner as in Examples 1 and 2. The evaluation results are shown in Table 1.
與圖5之簡易模型圖同樣地填充導熱性硬化性液狀樹脂組合物，與實施例1、2同樣地製作散熱結構體，並進行評價。將評價結果示於表1中。 The thermally conductive curable liquid resin composition was filled in the same manner as in the simple model diagram of FIG. 5, and a heat dissipation structure was produced in the same manner as in Examples 1 and 2, and evaluated. The evaluation results are shown in Table 1.
使用導熱性硬化性之聚矽氧樹脂組合物(信越化學工業股份有限公司製造，KE-4918，糊狀，濕氣硬化型，導熱率為0.9W/(m‧K))代替實施例1、2中所使用之導熱性硬化性液狀樹脂組合物，與實施例1、2同樣地進行評價。將評價結果示於表1中。 In place of Example 1, a thermally conductive curable polyoxynoxy resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KE-4918, paste, moisture-curing type, thermal conductivity: 0.9 W/(m‧K)) was used. The thermally conductive curable liquid resin composition used in 2 was evaluated in the same manner as in Examples 1 and 2. The evaluation results are shown in Table 1.
實施例1及比較例1-3係兩個發熱體之發熱量存在較大之差異的情形。關於配置高發熱量之電子零件之面的電磁波屏蔽殼體11a之溫度，比較例2、3與比較例1相比有所上升，與此相對，實施例1與比較例1相比有所下降。可知藉由導熱性硬化物僅配置於低發熱量之電子零件側，可抑制自高發熱量之電子零件產生之熱向電磁波屏蔽殼體11a傳導。進而，可知於實施例1中亦可抑制電子零件13a之溫度上升。 In the first embodiment and the comparative example 1-3, there is a case where there is a large difference in the amount of heat generation between the two heat generating bodies. The temperature of the electromagnetic wave shielding case 11a in which the surface of the electronic component having high heat generation was increased was compared with the comparative example 1 in Comparative Examples 2 and 3, whereas the first embodiment was lower than the comparative example 1. It is understood that the heat-conductive cured material is disposed only on the side of the electronic component having low heat generation, and the heat generated from the electronic component having high heat generation can be suppressed from being transmitted to the electromagnetic wave shielding case 11a. Further, it is understood that the temperature rise of the electronic component 13a can also be suppressed in the first embodiment.
又，實施例2及比較例4、5係兩個發熱體之發熱量幾乎無差異之情形。於此情形時，關於電磁波屏蔽殼體11a之溫度，比較例5與比較例4相比亦有較大上升，與此相對，實施例2與比較例4相比亦有所下降。即可知可抑制未配置導熱性硬化物之側的溫度上升。進而，可知於實施例2中，亦可抑制電子零件13a之溫度上升。 Further, in Example 2 and Comparative Examples 4 and 5, there was almost no difference in the amount of heat generation between the two heating elements. In this case, the temperature of the electromagnetic wave shielding case 11a was significantly higher than that of the comparative example 4 as compared with the comparative example 4, whereas the second embodiment was also lower than that of the comparative example 4. That is, it can be understood that the temperature rise on the side where the thermally conductive cured material is not disposed can be suppressed. Further, it is understood that in the second embodiment, the temperature rise of the electronic component 13a can be suppressed.
可知於使用導熱性聚矽氧樹脂組合物之實施例3、4中，亦可獲得與實施例1、2同樣之效果。 It is understood that the same effects as in Examples 1 and 2 can be obtained in Examples 3 and 4 in which the thermally conductive polyoxyxene resin composition is used.
由上述實施例及比較例確認：對於期望進一步散熱之印刷基板之正面側之高發熱量之發熱體，可藉由於印刷基板之背面側配置導熱性硬化物來抑制電磁波屏蔽殼體之頂壁，即期望散熱之發熱體之上方之溫度上升，同時亦抑制該發熱體之溫度上升。此意味著表示可藉由該導熱性硬化物之配置位置來控制傳熱方向。 In the above-described embodiment and the comparative example, it was confirmed that the heat generating body having a high heat generation amount on the front side of the printed circuit board which is desired to further dissipate heat can be disposed on the back side of the printed circuit board to suppress the top wall of the electromagnetic wave shielding case. The temperature above the heating element that is expected to dissipate increases, and the temperature rise of the heating element is also suppressed. This means that the heat transfer direction can be controlled by the arrangement position of the thermally conductive cured material.
11a、11b‧‧‧電磁波屏蔽殼體 11a, 11b‧‧‧ electromagnetic shielding housing
12‧‧‧印刷基板 12‧‧‧Printed substrate
13a、13b、13c、13d‧‧‧電子零件(發熱體) 13a, 13b, 13c, 13d‧‧‧Electronic parts (heating element)
14‧‧‧發熱體之周圍(亦可配置導熱性硬化性液狀樹脂組合物之硬化物的空間) 14‧‧‧War around the heating element (the space of the hardened material of the thermally conductive liquid resin composition may be disposed)
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